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Patented Oct. 28, 1952 STAT ES f rsN fiFH- F v METHOD OF'DYEING CELLULOS E ACETATE FIBERS A MIXED ACETATE-NYLON FABRIC USING AN AQUEOUS SOLUTION F AN ACID DYE, ETHYL ALCOHOL, AGE: TIC ACID, AND EITHER SODIUM 0 All I MONIUM THIOCYANATE, I

Henry Charles Olpin and Dora Louise Bell, Spondon, near Derby, England,assignors to Qelanese Corporation (if-America, a corporation-of Dela 1 ware No Drawing. Application Fanny 10, 1549, Sc

' 1 Claim.

I This invention relates to the colouration of textile materials comprising both fibres of cellulose acetate or other cellulose ester or ether'and fibres of-a superpo-lyamide. The term superpolyamide is used as including in particular superpolyurethanes and the superpolyamides obtainable by the self-condensation of amino fatty acids or by the condensation of aliphatic or other 'diami'nes with aliphatic or other dicarboxylic acids? The invention is particularly concerned with the colour'ation of materials cOIIlpllSlIlg on the one hand-cellulose acetate fibres and onthe other fibres of the superpolyamides obtainable byfco'ndensing a'dipic acid with hexamethylene diainina The latter condensation product is hereinafter referred to as nylon 66.

It'is' an object of the present invention to colour the cellulose acetate'of such a mixed material containing both cellulose acetate fibres and sup e'rpolyamide fibres with-out at the sam time colouring the latter fibres. Most of the dyes which are available for colouring cellulose lacetate fibres are also capable of colouring nylon 66 and other superpolyamide fibres; Thus the water-insoluble dyes which are so very largely, used in the-form of aqueous dispersions fo the colouring of cellulose acetate fibres are very useful for colouring nylon 66 fibres, since they yield as a rule more uniform shade-s than can be'obtained with the various acid dyes which have affinity for nylon 66. Again such acid dyes as colour cellulose acetate from aqueous baths o'clour nylon 66 even more readily. It would appear, therefora'to be a matter of some considerable difficulty tdcolqur the cellulose acetate;

fibres of a mixed material of the kind in question .yvithout at the same time colouring the nylon 66 fibres. Such a method would, however, be very useful, since it would facilitate the production of two-colour effects on textile fabrics containing, both cellulose acetate fibres and nylon 66 fibres. it would even be useful in the case of producing s'olid shades-on these mixed materials, since it "is not easy to find single dyes which dye cellulose acetate fibres to same shade as nylon 66;

fibres from one and the same bath. Apart from questions of depth of shade the tone is often l. quite "diiierent on nylon 66 from what it is on cellulose acetate. is' better to dye the cellulose acetate and nylon 66'- Quite frequently, therefore, it

in separate operations in spite of the fact that a solid shade is required.

It has been found that the aforesaid desirable results can be secured by applying to the mixed material dyes, for xample those water-insoluble results.

, be included in the dye liquid.

m1 No. 75,743. In Great Britain February 26, f j

dyes capable of dyeing cellulose acetate in the form of aqueous dispersions, in solutionina liquid medium which swells the cellulose acetate without substantially swelling the nylon 66. The

liquid medium is advantageously a mixture of water with a water-miscible organic liquid; It

hasbeen found that: aqueous ethyl alcohol or other alcohol of the formula CnH2n+1.OH,particularly one containing up to 3 or 4' carbon atoms, is a very effective medium for forming the dye solution, particularly whenxcontaining a proportion of athiocyanate.

As regards the concentration. of this, aqueous "alcohol, it has been found that, when using methyl, ethyl, n-propyl o isopropylg'alc'ohol, a concentration of by weight yields good Thethiocyanate, when: employed; may befor instance ammonium,'sod ium, potassium or zinc thiocyanate. The proportion of: the latter I may beof theorder of 11% to 5%, based on the water and alcohol together. A particularly effective mixture'for the purposes ofthe' invention -is ethyl alcohol of ;55 %'-75% strength byweight containing 1-5% e. g.about-2% or 3% of sodium 'or ammonium thiocyanate, the mixture being used at ordinary temperatures-of around 20"- A, small proportionof aller i Q d; f ample. formic, acetic or, p-ropionic acid, may-be included in the dye liquid. -The. "proportion should not be so high as to'cause the mixture to swell the nylon 66.. Thus, from 1% to 5% may Anvery effective mixture for the purposes of the invention consistsiof 0. c. of methylateldspirit, 240 .c. c. of water, 30 0. 0. of acetic acid and 20 gms. of sodium thiocyanate, together with the requisite dye. Using such a dye liquid containing a water-insoluble dye (at ordinary temperature) it is possible to col-our the cellulose acetate of a fabric containing both cellulose-acetate and nylon 66 while leaving-thelatter substantially -uncoloured.

In place of the alcohol/water mixtures-referred to above, other mixtures particularly aqueous mixtures which have the requisite swelling action on cellulose acetate without" undue swelling action on nylon 66-,may: be employed.

' Examples are mixturesof w-ater withwatermiscible ketones or esters, for. example acetone,

' diacetonealcohol, glycol monqacetate or ethyl lactate. Concentrations Qfathe-order of 20% to 50% will usually give the requisite solvent power for the dye and swelling action on the cellulose acetate. Aqueous diace-tone-alcohol of 30126 45% ylic-hydrox-yethyl-amide. "dyes can'be used and it i remarkablethat good raqueous baths.

3 strength by Weight may for instance be employed. Again there may be used a mixture of an alcohol, water, and acarboxylic ester which is not miscible in all proportions with water e. g.

methyl, ethyl or propyl esters of fo-rmi-o, acetic,

and propionic acids. An exampleiof such. a mixture is one of 40 parts of ethylacetate, 60:parts of ethyl alcohol (92% strengthbyweight) jahdiiZ parts of water. Non-aqueous liquids may also be used e. g. a mixture of a hydrocarbon with one of the above mentioned esters which are not mis-cible in all proportions with water,; e. .g. -a.mixt ure of ethyl acetate and xylene containing'10 or:80%

orrnore. :Ona largescaledyeingmay be effected 'ona jig. .Mechanical impregnation methods may be used thoughtherbestresults are obtained as a rule byeprovidingi for: a longer time of contact between'dyesolution and. material than is usually convenient when. employing such methods.

The dyesemployed may. be:any. f lt'h-QSB waterinsoluble rdyes whichyinsthe-form of aqueous dispersions, are capable of colouring cellulose acetate fibres. v.These. dyes may be ;of the nitrodiarylamine, azo, or amino-anthraquinone series. Examples are the .azo' :dye. obtainedlby coupling diazotised .p -amino-acetanilide with ,oor pphenyl-phenoL-the azodye from dia-zotisedvp A 'nitroaniline :and "-dl'. j (beta hydroxyethyl) 71mvohlor-aniline: 1-phenylaminoeanthraquinone, ;1- -amino 4 -'phenyleaminoeanthraquinone, and 1- amino-4-phenylaminoeanthraquinoneJ-carboxresist effects -can be v obtained ..on: the, nylon 66 when using aciddyes. --M0st acid :dyes, inaqueoussolutionehavegood afiinity fornylon 66. .Acid

dyes which can be used :are'Xylene Milling; Blue 6G, (Schultz, 7th edition, 1st supplement,.p..l.46),

Crocein Scarlet 3B8, (Color Index No. 252) ,*Azo Rubinol' 3GP, (Schultz, 7th edition,;2nd supplement, p 121) Neolan Orange R, .(AATCC Year -Book l947-48,- page 212) Coomassie. Brown :RS, solwa-y Ultra Blue BS, -(1 -amino-4-phenyl-.aminoanthraquinone-Z-sulphonic acid) ,and Supramine Green G, (Schultz, 7th edition; vol. 2, .p.f 203) Thereference-to Schultz isto the well known -Schultz"Farbstofitabellen," Tish edition. Anyof the foregoing dyes may be 1 used I as solutions of say 1 strength in the'methylated spirit/Water/ acetic acid/sodium thiocyanate mixture referred to above the;proportionsbeing flO/24/3/2 l as indicated.

Following the application of the dye solutions to the-textile-material by immersion-printing,

padding or other methods, the material is preferably'washed oil, for example first in cold water and then in warm-water. This removes adhering dye liquor from the fabric,- -butremoves little or no colour from the cellulose acetateportion. L'I-he "material may then be-dried in the-usual-way.

After colouring the cellulose acetate.portion of 1 the material, the latter may. then haveiits nylon 66 contenttcoloured; inz-any .suitable (way.v rF-Yor this purpose acid colours; or direct cotton cQlours which :have, aflinity for nylon 66' but little or no affinity for cellulcseacetate,canbeappliedas The dyeing may-be, of course,

Again, water-solubleatdflsl volume ratio containing:

o2 -Naphthalene-F Red us 0.1% Lissamine-F-Yellow2G8; (Schultz,--7th--edi- 4 carried out so as to obtain acontrastpf shade between the cellulose acetate fibres andthe nylon 66 fibres. Alternatively, the nylon 66 fibres may be dyed with acid or direct cotton dyes in the same shade as the cellulose acetate fibres. As already indicated,,this may be a convenient method of obtaining-asolid shade on the two fibres, since there are-verygfew dyes, particularly among the .-yellows, .orangesand reds, which dye nylon 66 in the same shade as they do cellulose acetate. .If.desire d, the, nylon 66 may be dyed before dye- .ing thecelluloseacetate portion of the material.

The fibres oflthe textile material coloured in accordance with the invention may be in the form of continuous filaments or in the form of staple fibres,;an;d:.both components of the material may be in-the same form or the two may be in difierent forms. The textile materials con- .taining the two kinds of fibres may be yarns or fabrics; yarns may be those spun from a mixture of cellulose acetate staple fibre ;and ;nylon 66 .staple fibre, orithose obtained-by doubling together two or -rnore yarns, at least, one of which is of cellulose;;-aoetate fibres while another is y of :nylon 66 fibres fabrics=may be those formed from yarns containing bothkinds of 3 fibres, or 2 those formed from Y cellulose acetate yarnson the one hand-and nylon .66 yarns -on-the other. ,Such

1 fabrics I may be jacquard -fabrics, for example jacquardfabrics woven from a nylonfiti twarpiand a. cellulose acetate-weft, so as to exhibit.a satin- ;fa e pattern o ny on 66 .u o erauniehwins both cellulos a e at ar and n on .1

yarns- Alterna vel the wa ma -.c sisw cellulose acetate;-yarns, and the resulting fabric exhibit a satin-faced pattern of celluloseacetate yarns ona grounder the two typesofyarns.

Example I {A fabric having a-warp of ny1on:66; and,-a ,weft

' of cellulose acetate is-immersedfor=five minutes "at-25 C. inasolution of the followin composition:

2100' cc.- methylated spirit 720cc. Water 90 cc; acetic acid 60; g. sodium thiocyanate 3/ g. l-pheny-lamino -anthraquinone 0.2 g; 2-nitro-4-chlordiphenylamine which colours the celluloseacetate .2. .d p. rose pink but leaves thenylon GB unstained. ..A f-ter rinsing thoroughly,-firstin cold and .then-inwarm :water, the fabric is dried,v and entered-into a bath tion, No; 736) 3% formic acid-(80% c don the ei ht n lthemet na Qr ih is continued-fen one hour; atAiO". ;C., and ;the;-pat

i erncw ll r nse .adzdrie .An T MRQ BY shad U h vin s pdxfastne riarpn rtie i produced @0 fabric. composed of celluloseraf etate yarns and. ylon 66. yarn imm 2on mins-, e

2 C in a i ture ofi i i fo owin qompqsit e 700 ccs. methylated spirit 240 cos. water .30 ccs..acetic acid 20;grs. sodiumthiocyanate 1G. grs- Croceine ScajrletBBS and thoroughly rinsed, first in cold, then in warm water and dried. The cellulose acetate is coloured a bright scarlet shade, while the nylon 66 is unstained, and if desired, may be dyed in self shade or contrasting shade with acid dye-stufis as described in Example I.

Example III grs. Solacet Fast Blue 238, (identical with Solway Ultra-Blue BS) and thoroughly rinsed, first in cold water, then in warm water, and dried. The cellulose acetate yarn is dyed a deep brilliant blue shade, while the nylon 66 is only very slightly tinted, and may be dyed in self or contrasting shades with acid dyestuffs as described in Example I.

Example IV A fabric composed of equal parts of cellulose acetate and nylon 66 yarns is immersed for 1 hour at 25 C. in a dyebath of the following composition:

400 ccs. diacetone alcohol 600 ccs. water grs. ammonium thiocyanate 2.5 grs. Artol Blue B, (corresponding with W001 Blue BL, Schultz, 7th edition, No. 9'74).

It is then thoroughly rinsed, first in cold, then in warm water, and dried. The cellulose acetate is dyed a medium shade of blue, whilst the nylon 66 is only slightly tinted.

The Artol Blue B may be replaced by Croceine Scarlet 3138 which gives a scarlet shade on the cellulose acetate leaving the nylon 66 white, or

by l-amino 4 phenylamine anthraquinone-2- carboxylic-hydroxyethyl-amide, which gives a full blue on the cellulose acetate, the nylon 66 being only tinted. I

Similar methods may be used for colouring analogous materials in which the cellulose acetate fibres are replaced by fibres of other cellulose esters or ethers, for example cellulose butyrate, propionate, acetobutyrate or acetopropionate, or in which the nylon 66 fibres are replaced by fibres of other superpolyamides.

Having described our invention, what We desire to secure by Letters Patent is:

Process for the coloration of textile material comprising both cellulose acetate fibers and fibers of a superpolyamide so as to color the former but leave the latter substantially uncolored, which comprises subjecting the material at ordinary temperatures to the action of a solution of an acid dye in aqueous ethyl alcohol of -75% strength by weight, said aqueous alcohol containing from 1-5% of acetic acid and from 1-5% of a compound selected from the group consisting of sodium and ammonium thiocyanates.

HENRY CHARLES OLPIN. DORA LOUISE BELL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,968,819 Dreyfus Aug. 7, 1934 2,292,433 Croft Aug. 11, 1942 2,428,835 Croft Oct. 14, 1947 OTHER REFERENCES American Dye. Report for January 28, 1946, pageP53. 

